CN107858663A - It is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene - Google Patents
It is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene Download PDFInfo
- Publication number
- CN107858663A CN107858663A CN201711125991.6A CN201711125991A CN107858663A CN 107858663 A CN107858663 A CN 107858663A CN 201711125991 A CN201711125991 A CN 201711125991A CN 107858663 A CN107858663 A CN 107858663A
- Authority
- CN
- China
- Prior art keywords
- copper powder
- graphene
- hydrogen
- copper
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
- C23C16/4581—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber characterised by material of construction or surface finish of the means for supporting the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention propose it is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, comprise the following steps：(1) catalyst layer is deposited in p type single crystal silicon upper surface；(2) carbon nano tube growth is carried out；(3) copper powder is placed on carbon nano pipe array surface；(4) 5min that anneals removes oxide on surface and copper crystal grain is grown up；(5) graphene growth is carried out, obtains the copper powder of graphene parcel.Be not in large area sintering while preventing copper powder from being blown off the advantage of the invention is that copper powder is placed on carbon nano pipe array using Van der Waals force.And can ensure that copper powder is intactly covered by few layer graphene using gaseous carbon sources and increase its antioxygenic property, the copper powder that graphene parcel is prepared using this method also ensure that its electric conductivity while its oxidation resistance in atmosphere is improved.
Description
Technical field
The present invention relates to it is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, more particularly to
Copper Powder Surface is by a kind of fully wrapped around method of graphene.
Background technology
Copper is all preferable metal material of a kind of electric conductivity and thermal conductivity, is used in the industry such as electric, mechanical.Copper at present
Powder especially copper nanoparticle is widely used in the fields such as conductive material, high-energy catalyst because of its unique performance.In addition,
Because the price of copper powder is much lower compared to inert metals such as gold, silver, so that it starts to be concerned.But naked copper powder is especially
It is that naked copper nanoparticle will soon be oxidized to cuprous oxide or cupric oxide in the environment of room temperature.Therefore copper powder is enabled
Enough it is widely used and has to solve the problems, such as that it is easily oxidized.Copper Powder Surface parcel graphene is a kind of preferable material, can
Slow down its oxidized speed while keep its electric conductivity.In copper powder anti-oxidant treatment, silane coupler wraps up the side of copper powder
Method can reduce its electric conductivity；Or the graphene grown is transferred to Copper Powder Surface, graphene can not be very with Copper Powder Surface
Its conductive and heat conductivility will be influenceed by contacting well.And not only solves its anti-oxidant problem in Copper Powder Surface direct growth graphene
And its electric conductivity and thermal conductivity will not be greatly lowered.
Graphene is a kind of new material, because its unique nano-meter characteristic is widely used in radiating, conduction etc.,
It has high-termal conductivity, high chemical stability, since graphene is found, it as added material come realize high-termal conductivity,
The research of high mechanical properties etc. receives much concern, but in Copper Powder Surface direct growth graphene and the research phase applied
To less.
He Yue brightness seminar of Central South University first using metallo-organic compound at 600 DEG C of horizontal stove dual temperature area chemical gas
Phase deposition process obtain multi-layer graphene parcel copper nanoparticle, at room temperature exposure in atmosphere 60 days its substantially do not aoxidized.
Zhao Naiqin seminars of University Of Tianjin are mutually tied by the use of PMMA as solid carbon source by ball milling and CVD thermal anneal process
The method of conjunction obtains Copper Powder Surface wrapped multiple graphene.From initial PMMA powder to PMMA liquid so that Copper Powder Surface is abundant
By graphene coated, copper and the compound material of graphene is successfully made, has improved its yield strength and tensile strength.
Switzerland Norman A Luchinger et al. are using the method for reproducibility flame in Copper Powder Surface growth in situ graphite
Alkene makes it have chemical inertness and stability, and then the copper powder that graphene wraps up is made to the ink of ink jet printing, obtain conduction
Property be more than 1S/cm circuit, in addition the printed circuit there is high chemical stability.
The content of the invention
It is contemplated that at least solves one of technical problem in correlation technique to a certain extent.
Therefore, it is an object of the present invention to propose one kind using CVD method directly in Copper Powder Surface coated graphite alkene
Method.
It is according to embodiments of the present invention it is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, including
Following steps：
(1) the having on the p type single crystal silicon of one layer of 200nm silica in 350 μ m-thicks using electron beam evaporation deposition machine
Catalyst layer is deposited in surface；
(2) using CVD in the 3min that annealed at 550 DEG C, carbon nano tube growth 4min is then carried out at 665 DEG C；
(3) copper powder is placed on to the carbon nano pipe array surface of step (2) acquisition, copper powder absorption is received in carbon by vibration
Nanotube surface, then remove unnecessary copper powder；
(4) copper powder in step (3) is put into vertical cold wall CVD with CNT, be passed through at 775 DEG C hydrogen and
Argon annealed 5min removes oxide on surface and copper crystal grain is grown up in order to graphene growth；
(5) methane, hydrogen and argon gas and then at 775 DEG C are passed through, wherein, methane carries out graphene life as gaseous carbon sources
Long, growth time 5min, hydrogen is reducibility gas, and argon gas is protective gas, last to be first down to 300 with 200 DEG C/min
DEG C, be then down in the air-flow of hydrogen and argon gas 150 DEG C be then turned on air pump close gas obtain graphene parcel copper powder.
Advantageously, in step (1), catalyst layer is 20nm aluminum oxide and 1nm iron
Advantageously, in step (2), reducing gas is flow velocity 700sccm hydrogen, and carbon-source gas are flow velocity 100sccm's
Acetylene.
Advantageously, in step (3), copper powder is the copper nanoparticle that surface is covered with sodium citrate dispersant.
Advantageously, the size of the copper powder is 15nm to 700nm.
Advantageously, in step (4), hydrogen flowing quantity 30sccm, argon flow amount 1000sccm.
Advantageously, in step (5), methane flow rate 10sccm, hydrogen flow rate 30sccm, argon gas flow velocity is
1000sccm。
It is according to embodiments of the present invention it is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, first
Copper powder is uniformly distributed on the carbon nanotubes, it is then uniform directly using gaseous carbon sources growth in situ using vertical cold wall CVD
Few layer graphene parcel copper powder.
The advantage of the invention is that copper powder is placed on carbon nano pipe array using Van der Waals force, prevent that copper powder from being blown off
While be not in large area sintering.And it can ensure that copper powder intactly covers increase by few layer graphene using gaseous carbon sources
Its antioxygenic property, the copper powder of graphene parcel is prepared while its oxidation resistance in atmosphere is improved using this method
It ensure that its electric conductivity.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
Fig. 1 is the SEM figures of the copper powder of sodium citrate dispersant parcel
Fig. 2 is the SEM figures of Copper Powder Surface parcel graphene after CVD growth
Fig. 3 a and Fig. 3 b are the partial enlargement SEM figures of Copper Powder Surface parcel graphene after CVD growth
Fig. 4 is the Raman figure that Copper Powder Surface wraps up graphene
Fig. 5 is that Copper Powder Surface wraps up the XRD after being exposed 90 days in graphene air
Fig. 6 pure copper powders are placed on silica surface and carry out the SEM figures after graphene growth
Fig. 7 pure copper powders are placed on silica surface and carry out the partial enlargement SEM figures after graphene growth
Embodiment
Embodiment 1
(1) the having on the p type single crystal silicon of one layer of 200nm silica in 350 μ m-thicks using electron beam evaporation deposition machine
Catalyst layer is deposited in surface, and the catalyst layer is 20nm aluminum oxide and 1nm iron；
(2) using CVD in the 3min that annealed at 550 DEG C, carbon nano tube growth 4min is then carried out at 665 DEG C, wherein
Reducing gas is hydrogen, flow velocity 700sccm, and carbon-source gas are acetylene, flow velocity 100sccm
(3) copper powder is placed on carbon nano pipe array surface, copper powder absorption is made in carbon nano tube surface by vibration, then
Remove unnecessary copper powder
(4) copper powder in step (3) is put into vertical cold wall CVD, hydrogen and argon annealed is passed through at 775 DEG C
5min removes oxide on surface and copper crystal grain is grown up in order to graphene growth, is then passed through methane as gas at 775 DEG C
Carbon source carries out graphene growth, and growth time 5min, wherein methane flow rate are 10sccm, last to be first down to 200 DEG C/min
300 DEG C, be then down in the air-flow of hydrogen and argon gas 150 DEG C be then turned on air pump close gas obtain graphene parcel copper
Powder, hydrogen flow rate 30sccm, argon gas flow velocity is 1000sccm, as shown in Fig. 2 its partial enlarged drawing is as shown in Figure 3.
(5) and then the copper powder to obtaining carries out phenetic analysis, shows that few layer graphene is present by the test of Fig. 4 Ramans, figure
The presence of 5XRD test surfaces graphene and simple substance copper crystal, while the exposure of 90 days is with the presence of some cuprous oxide.
Comparative example
Copper powder is directly placed at silicon oxide surface puts CVD stoves into and use the identical graphene conditioned growth of example 1, copper powder
Surface is wrapped up by graphene, as shown in Figure 6.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the different embodiments or example and the feature of different embodiments or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art is within the scope of the invention to above-mentioned implementation
Example is changed, changed, replacing and modification, each falls within protection scope of the present invention.
Claims (7)
1. it is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, it is characterised in that comprise the following steps：
(1) using electron beam evaporation deposition machine in the p type single crystal silicon upper surface with one layer of 200nm silica of 350 μ m-thicks
Catalyst layer is deposited；
(2) using CVD in the 3min that annealed at 550 DEG C, carbon nano tube growth 4min is then carried out at 665 DEG C；
(3) copper powder is placed on to the carbon nano pipe array surface of step (2) acquisition, copper powder absorption is made in CNT by vibration
Surface, then remove unnecessary copper powder；
(4) copper powder in step (3) is put into vertical cold wall CVD with CNT, hydrogen and argon gas is passed through at 775 DEG C
Annealing 5min removes oxide on surface and copper crystal grain is grown up in order to graphene growth；
(5) methane, hydrogen and argon gas and then at 775 DEG C are passed through, wherein, methane carries out graphene growth as gaseous carbon sources, raw
It is for a long time 5min, hydrogen is reducibility gas, and argon gas is protective gas, last to be first down to 300 DEG C with 200 DEG C/min, is connect
Be down in the air-flow of hydrogen and argon gas 150 DEG C be then turned on air pump close gas obtain graphene parcel copper powder.
2. the method as described in claim 1, it is characterised in that in step (1), catalyst layer is 20nm aluminum oxide and 1nm
Iron.
3. the method as described in claim 1, it is characterised in that in step (2), reducing gas is flow velocity 700sccm hydrogen,
Carbon-source gas are flow velocity 100sccm acetylene.
4. the method as described in claim 1, it is characterised in that in step (3), copper powder is that surface is covered with sodium citrate dispersant
Copper nanoparticle.
5. method as claimed in claim 4, it is characterised in that the size of the copper powder is 15nm to 700nm.
6. the method as described in claim 1, it is characterised in that in step (4), hydrogen flowing quantity 30sccm, argon flow amount is
1000sccm。
7. the method as described in claim 1, it is characterised in that in step (5), methane flow rate 10sccm, hydrogen flow rate is
30sccm, argon gas flow velocity are 1000sccm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711125991.6A CN107858663B (en) | 2017-11-15 | 2017-11-15 | A method of using CVD method directly in Copper Powder Surface coated graphite alkene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711125991.6A CN107858663B (en) | 2017-11-15 | 2017-11-15 | A method of using CVD method directly in Copper Powder Surface coated graphite alkene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107858663A true CN107858663A (en) | 2018-03-30 |
| CN107858663B CN107858663B (en) | 2019-06-11 |
Family
ID=61701812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711125991.6A Active CN107858663B (en) | 2017-11-15 | 2017-11-15 | A method of using CVD method directly in Copper Powder Surface coated graphite alkene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107858663B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110666159A (en) * | 2019-09-30 | 2020-01-10 | 上海元颉新材料科技有限公司 | Composite copper powder for acid degreasing process and preparation method and application thereof |
| CN113981410A (en) * | 2021-10-26 | 2022-01-28 | 化学与精细化工广东省实验室潮州分中心 | Antioxidant super-hydrophobic copper film and preparation method thereof |
| CN114854200A (en) * | 2022-05-17 | 2022-08-05 | 广东墨睿科技有限公司 | Preparation method of high-thermal-conductivity graphene composite thermal grease |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104053827A (en) * | 2011-12-09 | 2014-09-17 | 贝克休斯公司 | Method of forming carbonaceous particles and articles therefrom |
| CN106191805A (en) * | 2016-06-06 | 2016-12-07 | 重庆大学 | A kind of preparation method of magnetic graphene laminated film |
| CN106191804A (en) * | 2016-06-06 | 2016-12-07 | 重庆大学 | A kind of preparation method of magnetic graphene nano belt/graphene composite film |
-
2017
- 2017-11-15 CN CN201711125991.6A patent/CN107858663B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104053827A (en) * | 2011-12-09 | 2014-09-17 | 贝克休斯公司 | Method of forming carbonaceous particles and articles therefrom |
| CN106191805A (en) * | 2016-06-06 | 2016-12-07 | 重庆大学 | A kind of preparation method of magnetic graphene laminated film |
| CN106191804A (en) * | 2016-06-06 | 2016-12-07 | 重庆大学 | A kind of preparation method of magnetic graphene nano belt/graphene composite film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110666159A (en) * | 2019-09-30 | 2020-01-10 | 上海元颉新材料科技有限公司 | Composite copper powder for acid degreasing process and preparation method and application thereof |
| CN110666159B (en) * | 2019-09-30 | 2022-04-01 | 元颉新材料科技(浙江)有限公司 | Composite copper powder for acid degreasing process and preparation method and application thereof |
| CN113981410A (en) * | 2021-10-26 | 2022-01-28 | 化学与精细化工广东省实验室潮州分中心 | Antioxidant super-hydrophobic copper film and preparation method thereof |
| CN113981410B (en) * | 2021-10-26 | 2023-12-15 | 化学与精细化工广东省实验室潮州分中心 | Antioxidant super-hydrophobic copper film and preparation method thereof |
| CN114854200A (en) * | 2022-05-17 | 2022-08-05 | 广东墨睿科技有限公司 | Preparation method of high-thermal-conductivity graphene composite thermal grease |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107858663B (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yabuki et al. | Low-temperature synthesis of copper conductive film by thermal decomposition of copper–amine complexes | |
| JP6464461B2 (en) | Boron nitride fine particles and method for producing the same | |
| Renard et al. | Catalyst preparation for CMOS-compatible silicon nanowire synthesis | |
| CN107858663B (en) | A method of using CVD method directly in Copper Powder Surface coated graphite alkene | |
| CN105819710B (en) | A kind of graphene/basalt composite material and preparation method thereof | |
| CN108251076A (en) | Carbon nanotube-graphene composite radiating film, preparation method and application | |
| Shankar et al. | Synthesis of tungsten oxide (WO3) nanorods using carbon nanotubes as templates by hot filament chemical vapor deposition | |
| Cheng et al. | A SiCnw/PyC-toughened ZrB2-SiC coating for protecting Si-SiC coated C/C composites against oxidation | |
| Li et al. | Progress in large-scale production of graphene. Part 2: vapor methods | |
| JP2012506356A (en) | Metal / CNT- and / or fullerene composite coating on tape material | |
| Sahu et al. | Optical Property Characterization of Novel Graphene‐X (X= Ag, Au and Cu) Nanoparticle Hybrids | |
| CN108148452A (en) | A kind of composite heat-conducting filler containing graphene and its preparation method and application | |
| Luo et al. | Fabrication of W–Cu/La2O3 composite powder with a novel pretreatment prepared by electroless plating and its sintering characterization | |
| Rajarao et al. | GreenApproach to decorate multi-walled carbon nanotubes by metal/metal oxide nanoparticles | |
| Ma et al. | Controlled synthesis and optical properties of Cu/C core/shell nanoparticles | |
| Chiu et al. | Synthesis of ultra long vertically aligned carbon nanotubes using the rapid heating and cooling system in the thermal chemical vapor deposition process | |
| Qi et al. | Rapid low temperature sintering in air of copper submicron particles with synergistic surface-activation and anti-oxidative protection | |
| Shin et al. | Fabrication of multilayer graphene-coated copper nanoparticles for application as a thermal interface material | |
| KR20170023345A (en) | Method for preparing dispersion sol of boron nitride nanosheet by microwave heating and dispersion sol of boron nitride nanosheet prepared by the method | |
| Prekodravac et al. | Graphene quantum dots and fullerenol as new carbon sources for single–layer and bi–layer graphene synthesis by rapid thermal annealing method | |
| TWI312380B (en) | ||
| Varanasi et al. | Growth of high-quality carbon nanotubes on free-standing diamond substrates | |
| Ogawa et al. | Fabrication of carbon nanofiber-reinforced aluminum matrix composites assisted by aluminum coating formed on nanofiber surface by in situ chemical vapor deposition | |
| Wei et al. | Synthesis and Growth Mechanism of SiC/SiO 2 Nanochains Heterostructure by Catalyst‐Free Chemical Vapor Deposition | |
| JP2005075720A (en) | SiC-COATED CARBON NANOTUBE, MANUFACTURING METHOD THEREFOR AND COMPOSITE MATERIAL THEREOF |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |